CN105694078A - Anion-exchange membrane for fuel cells and preparation method thereof, and fuel cell using anion-exchange membrane - Google Patents
Anion-exchange membrane for fuel cells and preparation method thereof, and fuel cell using anion-exchange membrane Download PDFInfo
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Abstract
The invention discloses an anion-exchange membrane for fuel cells and a preparation method thereof, and a fuel cell using the anion-exchange membrane. The preparation method of the anion-exchange membrane comprises the following steps: mixing a polymer ionic liquid, a polymer monomer A and an emulsifier, dropwisely adding the mixture on a glass plate, putting the glass plate in a radiation field in a nitrogen atmosphere, carrying out radiation by a cobalt 60-gamma radiation process for 30-40 minutes to initiate polymerization radiation free radical reaction, and immersing the obtained polymer membrane in a 0.5-1 mol/L KOH solution at 50-60 DEG C for 60-78 hours to perform ion exchange; and finally, immersing the membrane in deionized water until the residual deionized water is neutral. The anion-exchange membrane disclosed by the invention has the advantages of favorable alkali resistance, favorable mechanical properties, higher ionic conductivity and higher heat stability.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of anion exchange membrane and preparation method thereof, be specifically related to a kind of fuel cell anion exchange membrane and preparation method thereof。
Background technology
Anion exchange membrane is the key position of anion-exchange membrane fuel cells, plays transmission anion in a fuel cell and intercepts the dual function of raw material。The quality of its performance directly affects the service life of fuel cell。
Excellent alkaline fuel cell polymer anion-exchange membrane is except possessing higher ionic conductivity, outside good heat stability and chemical stability, also to have good mechanical performance and alkali resistance。But, traditional quaternary polymer anion-exchange membrane heat stability and chemical stability are poor, and it eliminates reaction easily by Hofman under strong basicity environment, and the mechanism such as nucleophilic displacement of fluorine (SN2) and ylide conversion is degraded。It addition, quaternary polymer anion-exchange membrane introduces ion-exchange group through the process of chloromethylation mostly, and using severe toxicity carcinogen chloromethyl ether in chloromethylation process, environmental conservation and human health are had significant damage by this。These defects hinder the commercial applications of quaternary polymer anion-exchange membrane alkaline fuel cell。
In recent years, imidazole salt anion exchange membrane, due to the pi-conjugated effect of imidazole ring, had good chemical stability, caused the extensive concern of researchs。But, research finds, the anion exchange membrane based on imidazole salts also can be degraded under strongly alkaline conditions。
Accordingly, it would be desirable to seek more efficient way, preparation alkali resistance, satisfactory mechanical property, there is the fuel cell anion exchange membrane of higher ionic conductivity and good heat stability。
Summary of the invention
For overcoming defect of the prior art, the invention provides a kind of fuel cell anion exchange membrane and preparation method thereof。This film has good alkali resistance, mechanical performance, higher ionic conductivity and heat stability。
For reaching above-mentioned purpose, the technical solution used in the present invention is: a kind of fuel cell anion exchange membrane preparation method, comprises the steps:
1) vinyl imidazole is dissolved in acetonitrile with 1, the 3-dibromodiamantane waiting amount of substance, then adds KOH wherein, and at room temperature stirring 4-8 hour under nitrogen atmosphere。Then revolving steaming under vacuo, remove solvent, the crude product dichloromethane extraction obtained 3-5 time, then wash organic facies with deionized water, finally dewater with anhydrous magnesium sulfate, filter, rotation is steamed, and baking 12-24 hour at 30-40 DEG C in a vacuum, obtains aggretion type ionic liquid；
2) by step 1) in obtain aggretion type ionic liquid, polymerization type monomer A and emulsifying agent mixing, drip on a glass, put into radiation field under nitrogen atmosphere, adopt Co 60-gamma-radiation method radiation, exposure time 30-40 minute, there is polyreaction, by controlling distance controlling thicknesses of layers between glass plate；
3) by step 2) in the polymeric film for preparing be immersed in 0.5-1mol/LKOH solution at 50-60 DEG C 60-78 hour and carry out ion exchange。Finally by film bubble in deionized water until remaining deionized water reaches neutrality。
Described aggretion type ionic liquid structural formula is:
The mass ratio of described aggretion type ionic liquid, polymerization type monomer A and emulsifying agent is 3:1:0.1。
One or more in acrylonitrile, styrene, α-methyl styrene, methacrylonitrile, sulfonated phenylethylene, octafluorostyrene, methyl methacrylate, ethyl acrylate or methyl sulfonated phenylethylene of described polymer A。
Described emulsifying agent is selected from dodecylbenzene sodium sulfonate, polyoxypropylene polyethylene glycols ether, NPE。
Described polyreaction is radiation polymerization of radicals；
Described anion exchange membrane molecular weight is 10000-20000；
Described anion exchange membrane facing thickness is 20-30 micron；
A kind of fuel cell, it uses the anion exchange membrane in return film prepared by the method for described anion exchange membrane。
Owing to technique scheme is used, the present invention compared with prior art has the advantage that
(1) the fuel cell anion exchange membrane preparation method of present invention design is simple, it does not have use severe toxicity carcinogen chloromethyl ether and initiator, relatively environmental protection。
(2) the fuel cell anion exchange membrane of present invention design, diamantane (obsolete) plays the effect of cross-linking agent and electron-donating group, and the cross-linking type obtained all makes moderate progress based on imidazole salts anion exchange membrane alkali resistance, chemical stability and mechanical performance etc.。
(3) the fuel cell anion exchange membrane of present invention design, has higher electrical conductivity。
Detailed description of the invention
In order to make those skilled in the art be more fully understood that technical scheme, it is described in further detail below in conjunction with embodiment and to product of the present invention。
In the present embodiment, number-average molecular weight measures on Waters1515 gel permeation chrommatograph。
Embodiment 1:
A kind of fuel cell anion exchange membrane preparation method, comprises the steps:
1) vinyl imidazole (18.82g, 0.2mol) and 1,3-dibromodiamantane (29.4g, 0.1mol) are dissolved in acetonitrile (113g), then add 25gKOH wherein, and at room temperature stirring 4 hours under nitrogen atmosphere。Then revolving steaming under vacuo, remove solvent, the crude product dichloromethane extraction obtained 5 times, then wash organic facies with deionized water, finally dewater with anhydrous magnesium sulfate, filter, rotation is steamed, and dries 12 hours at 40 DEG C in a vacuum, obtains aggretion type ionic liquid；
2) by step 1) in the aggretion type ionic liquid 30g, the methyl methacrylate 10g that obtain and emulsifying agent polyoxypropylene polyethylene glycols ether 1g mixing, drop on the glass plate of 20 microns, put into radiation field under nitrogen atmosphere, adopt Co 60-gamma-radiation method radiation, exposure time 35 minutes, obtaining number-average molecular weight is 10000, and thickness is the polymeric film of 20 microns；
3) by step 2) in the polymeric film for preparing be immersed in 1mol/LKOH solution at 60 DEG C 60 hours and carry out ion exchange。Finally by film bubble in deionized water until remaining deionized water reaches neutrality。
Embodiment 2
A kind of fuel cell anion exchange membrane preparation method, comprises the steps:
1) vinyl imidazole (18.82g, 0.2mol) and 1,3-dibromodiamantane (29.4g, 0.1mol) are dissolved in acetonitrile (113g), then add 30gKOH wherein, and at room temperature stirring 4 hours under nitrogen atmosphere。Then revolving steaming under vacuo, remove solvent, the crude product dichloromethane extraction obtained 3-5 time, then wash organic facies with deionized water, finally dewater with anhydrous magnesium sulfate, filter, rotation is steamed, and baking 12 hours at 40 DEG C in a vacuum, obtains aggretion type ionic liquid；
2) by step 1) in the aggretion type ionic liquid 30g, the acrylonitrile 10g that obtain and emulsifying agent dodecylbenzene sodium sulfonate 1g mixing, drop on the glass plate of 30 microns, put into radiation field under nitrogen atmosphere, adopt Co 60-gamma-radiation method radiation, it is 15000 that exposure time obtains number-average molecular weight for 40 minutes, and thickness is the polymeric film of 30 microns；
3) by step 2) in the polymeric film for preparing be immersed in 1mol/LKOH solution at 60 DEG C 72 hours and carry out ion exchange。Finally by film bubble in deionized water until remaining deionized water reaches neutrality。
Embodiment 3
A kind of fuel cell anion exchange membrane preparation method, comprises the steps:
1) by vinyl imidazole (18.82g, 0.2mol) it is dissolved in acetonitrile (112.92g) with 1,3-dibromodiamantane (29.4g, 0.1mol), add 22.4gKOH more wherein, and at room temperature stirring 4 hours under nitrogen atmosphere。Then revolving steaming under vacuo, remove solvent, the crude product dichloromethane extraction obtained 3 times, then wash organic facies with deionized water, finally dewater with anhydrous magnesium sulfate, filter, rotation is steamed, and dries 12 hours at 30 DEG C in a vacuum, obtains aggretion type ionic liquid；
2) by step 1) in the aggretion type ionic liquid 30g, the sulfonated phenylethylene 10g that obtain and emulsifying agent NPE 1g mixing, drop on the glass plate of 22 microns, put into radiation field under nitrogen atmosphere, adopt Co 60-gamma-radiation method radiation, exposure time 30 minutes, polyreaction occurs, and obtaining number-average molecular weight is 12000, and thickness is the polymeric film of 22 microns；；
3) by step 2) in the polymeric film for preparing be immersed in 0.5mol/LKOH solution at 50 DEG C 60 hours and carry out ion exchange。Finally by film bubble in deionized water until remaining deionized water reaches neutrality。
Embodiment 4
A kind of fuel cell anion exchange membrane preparation method, comprises the steps:
1) vinyl imidazole (18.82g, 0.2mol) and 1,3-dibromodiamantane (29.4g, 0.1mol) are dissolved in acetonitrile (112.92g), then add 28gKOH wherein, and at room temperature stirring 8 hours under nitrogen atmosphere。Then revolving steaming under vacuo, remove solvent, the crude product dichloromethane extraction obtained 5 times, then wash organic facies with deionized water, finally dewater with anhydrous magnesium sulfate, filter, rotation is steamed, and dries 24 hours at 40 DEG C in a vacuum, obtains aggretion type ionic liquid；
2) by step 1) in the aggretion type ionic liquid 30g, the octafluorostyrene 10g that obtain and emulsifying agent dodecylbenzene sodium sulfonate 1g mixing, drop on the glass plate of 25 microns, put into radiation field under nitrogen atmosphere, adopt Co 60-gamma-radiation method radiation, exposure time 40 minutes, polyreaction occurs, and obtaining number-average molecular weight is 13000, and thickness is the polymeric film of 25 microns；；
3) by step 2) in the polymeric film for preparing be immersed in 1mol/LKOH solution at 60 DEG C 78 hours and carry out ion exchange。Finally by film bubble in deionized water until remaining deionized water reaches neutrality。
Embodiment 5
A kind of fuel cell anion exchange membrane preparation method, comprises the steps:
1) vinyl imidazole (18.82g, 0.2mol) and 1,3-dibromodiamantane (29.4g, 0.1mol) are dissolved in acetonitrile (112.92g), then add 30gKOH wherein, and at room temperature stirring 6 hours under nitrogen atmosphere。Then revolving steaming under vacuo, remove solvent, the crude product dichloromethane extraction obtained 3 times, then wash organic facies with deionized water, finally dewater with anhydrous magnesium sulfate, filter, rotation is steamed, and dries 18 hours at 35 DEG C in a vacuum, obtains aggretion type ionic liquid；
2) by step 1) in the aggretion type ionic liquid 30g, the octafluorostyrene 10g that obtain and emulsifying agent NPE 1g mixing, drop on the glass plate of 23 microns, put into radiation field under nitrogen atmosphere, adopt Co 60-gamma-radiation method radiation, exposure time 36 minutes, polyreaction occurs, and obtaining number-average molecular weight is 18000, and thickness is the polymeric film of 23 microns；；
3) by step 2) in the polymeric film for preparing be immersed in 0.8mol/LKOH solution at 55 DEG C 72 hours and carry out ion exchange。Finally by film bubble in deionized water until remaining deionized water reaches neutrality。
Meanwhile, in order to assess the concrete technique effect of fuel cell anion exchange membrane of the present invention, from aspects such as ionic conductivity, tensile property and alkali resistances, the specific performance of embodiment 1～5 is tested respectively。Electrical conductivity adopts two electrode AC impedance methods to record on electrochemical workstation (ZahnerIM6EX), the alkali resistance test of film is to be immersed in by film in the 1mol/LKOH aqueous solution at 80 DEG C 60 days, calculates what the rate of change of electrical conductivity before and after soaking was weighed。Computing formula is: electrical conductivity after electrical conductivity-immersion before rate of change=immersion)/soak front electrical conductivity。The tensile property of film universal model machine (InstronModel3365) is tested at 25 DEG C, and rate of extension is 5mm/min。Each sample test 3 times, finally gives a meansigma methods。Concrete test data are as shown in table 1:
The different embodiment specific performance test data of table 1
As can be seen from Table 1, the present invention prepares in the 1mol/LKOH being immersed at 80 DEG C of the anion exchange membrane of gained that after 60 days, degradation rate is less than 1.5%, and before and after soaking, electrical conductivity is all higher than 0.03Scm-1, hot strength is not less than 36MPa, and elongation at break is not less than 160MPa。And in the 1mol/LKOH aqueous solution that traditional anion exchange membrane is at 80 DEG C after 30 days degradation rate at 1～%, electrical conductivity 0.01～.027Scm-1, hot strength 18～0Mpa, elongation at break 65～16%。By contrast, the anion exchange membrane of present invention performance indications in ionic conductivity, tensile property and alkali resistance etc. all have lifting, it is possible to it is applied in alkaline fuel cell。
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction；The those of ordinary skill of all industry all can shown in by specification and the above and implement the present invention swimmingly；But, all those skilled in the art without departing within the scope of technical solution of the present invention, available disclosed above technology contents and make a little change, modify and the equivalent variations of differentiation, be the Equivalent embodiments of the present invention；Meanwhile, all change of any equivalent variations, modification and differentiation etc. above example made according to the substantial technological of the present invention, all still fall within the protection domain of technical scheme。
Claims (8)
1. the preparation method of a fuel cell anion exchange membrane, it is characterised in that comprise the following steps:
1) 1,3-dibromodiamantane of vinyl imidazole with amount of substance such as grade is dissolved in acetonitrile, then adds KOH wherein, and at room temperature stirring 4-8 hour under nitrogen atmosphere, then revolve steaming under vacuo, remove solvent, the crude product obtained, then thick product dichloromethane extraction 3-5 time, then wash organic facies with deionized water, finally dewater with anhydrous magnesium sulfate, filter, rotary evaporation, and dry 12-24 hour at 30-40 DEG C in a vacuum, obtain aggretion type ionic liquid；
2) by step 1) in the aggretion type ionic liquid, polymerization type monomer A and the emulsifying agent that obtain mix according to mass ratio 3:1:0.1, drip on a glass, put into radiation field under nitrogen atmosphere, adopt Co 60-gamma-radiation method radiation, exposure time 30-40 minute, polyreaction is occurred to obtain polymeric film；
3) by step 2) in the polymeric film for preparing be immersed in the KOH solution of 0.5-1mol/L at 50-60 DEG C 60-78 hour and carry out ion exchange, finally by polymeric film film bubble in deionized water until remaining deionized water reaches neutrality；
Described aggretion type leaving office liquid is:
One or more in acrylonitrile, styrene, α-methyl styrene, methacrylonitrile, sulfonated phenylethylene, octafluorostyrene, methyl methacrylate, ethyl acrylate or methyl sulfonated phenylethylene of described polymerization type monomer A, described polyreaction is radiation polymerization of radicals。
2. the preparation method of anion exchange membrane according to claim 1, it is characterised in that: described emulsifying agent is selected from dodecylbenzene sodium sulfonate, polyoxypropylene polyethylene glycols ether, NPE。
3. the preparation method of anion exchange membrane according to claim 1, it is characterised in that: step 1) described in 2-3 times that amount of substance is vinyl imidazole amount of substance of KOH。
4. the preparation method of anion exchange membrane according to claim 1, it is characterised in that: step 1) described in the quality of acetonitrile be 6-10 times of vinyl imidazole。
5. adopt the anion exchange membrane that the preparation method of claim 1 prepares。
6. anion exchange membrane according to claim 5, it is characterised in that: described anion exchange membrane number-average molecular weight 10000-20000。
7. the anion exchange membrane according to claim 5 or 6, it is characterised in that: described anion exchange film thickness is 20-30 micron。
8. the fuel cell for preparing the anion exchange membrane in return film prepared by the method for anion exchange membrane used described in any one of claim 1～4。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108199067A (en) * | 2018-01-02 | 2018-06-22 | 泰顺永庆电力技术有限公司 | A kind of high alkali resistance is based on benzoglioxaline salt anion-exchange membrane and preparation method thereof |
| CN108232225A (en) * | 2018-01-02 | 2018-06-29 | 泰顺永庆电力技术有限公司 | A kind of diaphragm of vanadium cell containing adamantane structure and preparation method thereof |
| CN108219086A (en) * | 2018-01-02 | 2018-06-29 | 泰顺永庆电力技术有限公司 | One kind is based on fullerene anion exchange membrane and preparation method thereof |
| CN109612808A (en) * | 2019-02-13 | 2019-04-12 | 王丽丽 | A kind of hydrophilic glass slide for medicine detection |
| CN109860675A (en) * | 2019-01-08 | 2019-06-07 | 杨记周 | A kind of new-energy automobile fuel cell ion exchange membrane and preparation method thereof |
| US12018104B2 (en) | 2018-12-11 | 2024-06-25 | 3M Innovative Properties Company | Copolymers with cationic, nitrogen-containing groups and anion exchange membranes made therefrom |
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| CN101844042A (en) * | 2010-05-21 | 2010-09-29 | 厦门大学 | Preparation method of anion-exchange membranes based on ionic liquid |
| CN102122720A (en) * | 2011-01-25 | 2011-07-13 | 厦门大学 | Fluorine-containing acrylate polymer anion exchange membrane and preparation method thereof |
| CN102382293A (en) * | 2011-08-05 | 2012-03-21 | 苏州大学 | Polymer anion exchange membrane and preparation method thereof |
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| CN103304832A (en) * | 2013-06-07 | 2013-09-18 | 常州大学 | Preparation method of anion exchange membrane based on biimidazole cation cross-linking agent |
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| CN108199067A (en) * | 2018-01-02 | 2018-06-22 | 泰顺永庆电力技术有限公司 | A kind of high alkali resistance is based on benzoglioxaline salt anion-exchange membrane and preparation method thereof |
| CN108232225A (en) * | 2018-01-02 | 2018-06-29 | 泰顺永庆电力技术有限公司 | A kind of diaphragm of vanadium cell containing adamantane structure and preparation method thereof |
| CN108219086A (en) * | 2018-01-02 | 2018-06-29 | 泰顺永庆电力技术有限公司 | One kind is based on fullerene anion exchange membrane and preparation method thereof |
| CN108219086B (en) * | 2018-01-02 | 2020-11-03 | 泰顺永庆电力技术有限公司 | Anion exchange membrane based on fullerene and preparation method thereof |
| CN108199067B (en) * | 2018-01-02 | 2020-11-03 | 泰顺永庆电力技术有限公司 | High-alkali-resistance benzimidazole salt-based anion exchange membrane and preparation method thereof |
| US12018104B2 (en) | 2018-12-11 | 2024-06-25 | 3M Innovative Properties Company | Copolymers with cationic, nitrogen-containing groups and anion exchange membranes made therefrom |
| CN109860675A (en) * | 2019-01-08 | 2019-06-07 | 杨记周 | A kind of new-energy automobile fuel cell ion exchange membrane and preparation method thereof |
| CN109860675B (en) * | 2019-01-08 | 2020-12-01 | 戴金燕 | New energy automobile fuel cell ion exchange membrane and preparation method thereof |
| CN109612808A (en) * | 2019-02-13 | 2019-04-12 | 王丽丽 | A kind of hydrophilic glass slide for medicine detection |
Also Published As
| Publication number | Publication date |
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| CN108794784A (en) | 2018-11-13 |
| CN105694078B (en) | 2018-08-24 |
| CN108794784B (en) | 2021-06-22 |
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